CN103058239A - Method of extracting aluminum oxide and white carbon black from pulverized fuel ash - Google Patents
Method of extracting aluminum oxide and white carbon black from pulverized fuel ash Download PDFInfo
- Publication number
- CN103058239A CN103058239A CN2013100385654A CN201310038565A CN103058239A CN 103058239 A CN103058239 A CN 103058239A CN 2013100385654 A CN2013100385654 A CN 2013100385654A CN 201310038565 A CN201310038565 A CN 201310038565A CN 103058239 A CN103058239 A CN 103058239A
- Authority
- CN
- China
- Prior art keywords
- flyash
- aluminum oxide
- residue
- carbon black
- white carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention provides a method of extracting aluminum oxide and white carbon black from pulverized fuel ash. The method comprises the steps of: extracting amorphous silicon dioxide by sodium hydroxide, separating silicic acidin a carbonation manner, recovering sodium carbonate, sintering residues, extracting aluminum oxide by hydrochloric acid and separating silicid acid, so that silicon dioxide and aluminum oxide are effectively extracted from the pulverized fuel ash and are used for producing the white carbon black and the aluminum oxide. According to the method, the silicon dioxide and aluminum oxide of above 95 percent can be extracted from the pulverized fuel ash, few waste residues are generated, and sodium carbonate and carbon dioxide generated in a process can be recycled so that the production cost is greatly reduced. The method has the advantages of reasonable design, simple process, low material consumption and energy consumption, few residues and is a clean production technology.
Description
Technical field
The present invention relates to the comprehensive utilization of flyash, be specifically related to a kind of method of from flyash, extracting aluminum oxide and white carbon black.
Background technology
Coal has produced a large amount of flyash in combustion processes, havoc ecotope.Flyash is mainly used in building the devalued aspects such as worker, building materials at present, utilizes approach single, and utilization is limited, and the higher value application that carries out flyash is the effective way that solves the flyash pollution problem.
Flyash contains abundant aluminum oxide and silicon-dioxide, extracts aluminum oxide and silicon-dioxide and prepare the important directions that high added value aluminium, silicon product become the flyash higher value application from flyash.The typical process of extracting aluminum oxide and silicon-dioxide from flyash is using acid and alkali combination method, namely utilize hydrochloric acid or sulfuric acid first the alumina dissolution in the flyash to be formed water miscible aluminum salt solution, remaining residue is mainly take silicon-dioxide as main, change into sodium silicate solution with sodium hydroxide under high-temperature and high-pressure conditions again, aluminum salt solution and sodium silicate solution be further trans-utilization again.But because flyash mainly exists with Vitrea forms of ferro-silicon-aluminium such as mullite, melilith, sodalite and spinel ferrites, structure is highly stable, the non-constant of reactive behavior, thereby, direct extraction makes the extraction yield of aluminum oxide and silicon-dioxide low, the soda acid consumption is large, has limited the further utilization of this technology.
" utilizing flyash to produce aluminium hydroxide and silicic acid processing method " (number of patent application 200710133216.5) (document 1) of Liu Chengchang invention adopts " soda ash alkali melts-caustic soda alkali fusion-hydrolysis-carbonization-causticization " technique, and 95% aluminum oxide and 90% silicon-dioxide are extracted in realization simultaneously.But this technical process is complicated, and condition is harsh, and operation easier is large, and cost is high.
" utilizing aluminous fly-ash to produce aluminum oxide and white carbon black process for cleanly preparing " (number of patent application 200710087028.3) (document 2) of horse great writing invention used sour acidleach with yellow soda ash and flyash after 750 ~ 880 ° of C calcinings, obtain aluminum salt solution and silicic acid, further prepare aluminium, silicon product." a kind of method of from flyash, extracting high-purity alpha-alumina and silica gel " (number of patent application 201010013749.1) (document 4) of " from flyash, extracting the method for high purity aluminium oxide and silica gel " (number of patent application 200810017869.1) (document 3) of similar technique such as Pan Aifang invention and Ma Yuzhao invention.This technique can make that the extraction yield of aluminum oxide and silicon-dioxide all can reach more than 90% in the flyash.But the method is subject to the restriction of chemical reaction, and acid, alkali consumption is large, and can not circulate, and raw materials cost is too high, has limited the commercial application of this technology.
" a kind of method of utilizing flyash to produce silicon-dioxide and aluminum oxide " (number of patent application 200710062534.7) (document 5) of Pingshuo Coal Industry Corp. invention and the method for firstly extracting silicon and secondly extracting aluminum " a kind of from flyash " (number of patent application 200710061662.X) (document 6) extract SiO in the flyash with NaOH first
2, allocate CaO or CaCO in the slag after carrying silicon again
3Then sintering adopts Bayer process to extract aluminum oxide.The method can produce a large amount of slags, and the extraction yield of aluminum oxide is not high yet.
To sum up, the technology of exploitation is owing to exist the problem of the several respects such as aluminium silicon extraction yield is low, raw material consumption is large, technical process is complicated, the generation level of residue is large at present, make production cost high, produce secondary pollution, cause from flyash, extracting the technical costs height of aluminum oxide and silicon-dioxide, be difficult to realize commercial application.
Summary of the invention
The object of the invention is to overcome the shortcoming that prior art exists, a kind of method of extracting aluminum oxide and white carbon black from flyash is provided, the method production cost is low, product yield is high, the quantity of slag is little.
The present invention is achieved through the following technical solutions, and its concrete steps are:
(1) amorphous silicon di-oxide extracts: the amorphous silicon di-oxide with in the sodium hydroxide solution lixiviate flyash forms sodium silicate solution and residue.
(2) carbonating is separated silicic acid: the sodium silicate solution that step (1) is obtained passes into carbonic acid gas and carries out carbonating, obtain sodium carbonate solution and siliceous colloid after the filtering separation, sodium carbonate solution is by condensing crystal and add unslaked lime causticization recovery yellow soda ash and sodium hydroxide.
(3) batching: the residue that step (1) is obtained mixes with the yellow soda ash that former flyash and step (2) reclaim, and obtains batching.
(4) sintering: the batching sintering with step (3) obtains sintered clinker, the CO in the sintering process
2Be back to the carbonating operation of step (2).
(5) hydrochloric acid acidleach: with the sintered clinker hydrochloric acid acidleach that step (4) obtains, separate obtaining aluminum salt solution and siliceous colloid.
(6) alumina preparation: the aluminum salt solution that step (5) is obtained obtains aluminum oxide by adding alkali removal of impurities, carbonization, drying, calcining.
(7) white carbon black preparation: with the siliceous colloid that step (2) and step (5) obtain wash, drying makes white carbon black.
The middle NaOH of described step (1) and flyash is 0.2 ~ 1:1 proportioning in mass ratio; The mass concentration of NaOH solution is 20-40%; Temperature of reaction is 80 ~ 150 ° of C.
Batching is according to Al in residue and the former flyash in the described step (3)
2O
3And SiO
2Content press the aluminium silicon mol ratio and determine, be specially:
I. work as aluminium silicon mol ratio in the residue〉1.2, residue and former flyash are made into compound in proportion, making aluminium silicon mol ratio wherein is 0.9 ~ 1.2; Yellow soda ash mixes by Na:Al mol ratio 1 ~ 2 with compound again, and preferred 1.1 ~ 1.5;
Ii. the aluminium silicon mol ratio is 0.9 ~ 1.2 in residue, residue is mixed preferred 1.1 ~ 1.5 by Na:Al mol ratio 1 ~ 2 with yellow soda ash.
Iii. residue and yellow soda ash are pressed first 1 ~ 2 times of [n of molar fraction of Na in aluminium silicon mol ratio＜0.9 in the residue
Al+ 2(n
Si-n
Al)] proportioning, preferred 1.1 ~ 1.5[n
Al+ 2(n
Si-n
Al)] proportioning, wherein, n
AlAnd n
SiBe respectively the molar fraction of aluminium in the residue, silicon.
Sintering temperature is 700 ~ 950 ° of C in the described step (4), preferred 800 ~ 900 ° of C.
Compared with prior art advantage of the present invention and effect:
The present invention utilizes and contains a large amount of amorphous Si O in the flyash
2Characteristics, set up in advance lixiviate part of employing NaOH solution SiO
2Improve the alumina silica ratio of flyash, with the yellow soda ash that produces in the process and residue sintering after batching of carrying behind the silicon, sintered material be used for to extract the novel process of aluminum oxide and remaining silicon-dioxide, has overcome that existing flyash extracts that aluminium in aluminum oxide and the silicon-dioxide technology, silicon extraction yield are low, complex process, drawback that raw material consumption is large.Owing to the yellow soda ash and all recyclable and recycles of carbonic acid gas that produce in the production process, obviously saved the raw material consumption of process, greatly reduce production cost, and the waste residue amount that produces is few, the extraction yield of aluminum oxide and silicon-dioxide all can reach more than 95%.In a word, the present invention is reasonable in design, technique is simple, the material consumption energy consumption is little, residue is few, is a kind of process for cleanly preparing.
Figure of description
Fig. 1 is the process flow sheet that flyash is produced white carbon black and aluminum oxide.
Embodiment
Below in conjunction with the technical process (see figure 1) with the present invention is extracted aluminum oxide to reaction formula from flyash and white carbon black is described in further details:
(1) amorphous silicon di-oxide extracts
Aluminium silicon mol ratio in the flyash is little, and generally between 0.3 ~ 0.9, high silicone content can strengthen consumption of raw materials, and is unfavorable to carrying aluminium.The amorphous Si O that suitable content is arranged in the flyash
2, and non-crystalline state SiO
2Reactive behavior very high.The present invention adopts the lixiviate of sodium hydroxide solution elder generation to go out amorphous silicon di-oxide in the part flyash, improves alumina silica ratio, is beneficial to the follow-up aluminium of carrying.
Adopt the reaction of sodium hydroxide solution and amorphous silicon di-oxide, form sodium silicate solution and residue.
The correlated response that occurs:
2NaOH+SiO
2→Na
2SiO
3+H
2O ①
(2) carbonating is separated silicic acid:
The sodium silicate solution that step (1) is obtained passes into carbonic acid gas and carries out carbonating, obtains sodium carbonate solution and siliceous colloid after the filtering separation, and sodium carbonate solution is by condensing crystal and add the unslaked lime causticization and reclaim yellow soda ash and sodium hydroxide.
The correlated response that occurs:
Na
2SiO
3+CO
2+H
2O→Na
2CO
3+H
2SiO
3 ②
Na
2CO
3+CaO+H
2O→2NaOH+CaCO
3 ③
(3) batching and sintering:
Yellow soda ash and aluminium silicate mineral sintering, the reaction of generation:
Na
2CO
3+ Al
2O
3+ 2SiO
2→ 2NaAlSiO
4(nepheline)+CO
24.
The side reaction that occurs:
Na
2CO
3+ SiO
2→ Na
2SiO
3+ CO
2(residue Al:Si＜1) 5.
Na
2CO
3+ Al
2O
3→ 2NaAlO
2+ CO
2(residue Al:Si〉1) 6.
Aluminium silicon mol ratio in the former flyash is generally 0.3 ~ 0.9, silicon is obviously excessive, can 4. and 5. react by reaction formula, the mol ratio of Na:Al:Si reaction is 1:1:1 in the reaction 4., namely 1 mole of Al and 1 mole of Si only consume respectively 0.5 mole of Na, and 5. excessive silicon-dioxide can carry out by formula, and 1 mole of Si can consume 2 moles of Na, obviously strengthens alkaline consumption.
This technique is used first the amorphous SiO of alkali lixiviate part
2, improve the alumina silica ratio in the raw material, reduce unnecessary SiO in the sintering reaction
2Alkaline consumption.By reaction 1., although 1 mole of Si also can consume 2 moles of Na, separate the silicic acid operation in carbonating and can generate Na
2CO
3(formula 2.) can reclaim Na by condensing crystal and unslaked lime causticization
2CO
3And NaOH, the Na of recovery
2CO
3Can be used for sintering reaction, NaOH is back to alkali and soaks reaction, thereby reduces alkaline consumption.
Pre-lixiviate SiO
2After, the alumina silica ratio in the former flyash improves, if alumina silica ratio is 1, then 4. reacts by formula, and 1 mole of Al and 1 mole of Si only consume respectively 0.5 mole of Na, reach the purpose of low alkaline consumption.If silicon or aluminium is excessive, then 5. or 6. excessive silicon or aluminium can carry out by formula with yellow soda ash, and 1 mole of Si consumes 2 moles of Na, and 1 mole of Al consumes 1 mole of Na, all increases alkaline consumption.If but aluminium is excessive, can by with former flyash prepare burden to alumina silica ratio be about 1,4. main body reaction is occured by formula, then can reduce alkaline consumption.If the aluminium silicon mol ratio less than 1, except 4. reacting by formula, although 5. unnecessary silicon can react by formula, is compared with former flyash, alumina silica ratio still is improved, and alkaline consumption reduces.
Sintering reaction carries out at 700 ~ 950 ° of C, obtains sintered clinker.CO in the sintering process
2Be back to the carbonating operation of step (1).
(4) hydrochloric acid acidleach:
With the sintered clinker hydrochloric acid acidleach that step (3) obtains, separate obtaining aluminum salt solution and siliceous colloid.
The correlated response that occurs:
4HCl+NaAlSiO
4(nepheline) → NaCl+AlCl
3+ H
2SiO
3+ H
2O 7.
2HCl+Na
2SiO
3→2NaCl+H
2SiO
3 ⑧
4HCl+NaAlO
2→NaCl+AlCl
3+2H
2O ⑨
(5) alumina preparation:
The aluminum salt solution that step (4) is obtained obtains aluminum oxide by adding alkali removal of impurities, drying, calcining.Adding alkali removal of impurities main process is that adding NaOH to pH is filtration in 6 o'clock in aluminum salt solution, and filtrate is waste liquid, and the solid filtrate is Al (OH)
3And Fe (OH)
3Mixture, then this mixture is dissolved with NaOH, and to add alkali be to filter to pH that filtrate is NaAlO at 10 o'clock
2Solution, filter residue are Fe (OH)
3, with NaAlO
2Solution carbon divides acquisition Al (OH)
3, 110 ° of C dryings, 1200 ° of C calcinings obtain aluminum oxide.
(6) white carbon black preparation:
The siliceous colloid washing that step (1) and step (4) are obtained, 110 ° of C dry white carbon blacks.
Below the present invention will be further described by specific embodiment, but protection scope of the present invention is not limited only to following examples.
Embodiment 1
Getting the 100g alumina content is 35.4%, and dioxide-containing silica is 51.3% flyash, according to step of the present invention:
(1) amorphous silicon di-oxide extracts:
Getting sodium hydroxide 60g, to be configured to mass concentration be 20% sodium hydroxide solution, and with the amorphous silicon di-oxide in this solution lixiviate flyash, at 95 ° of C reaction 5h, solid-liquid separation forms sodium silicate solution and residue, and the residue quality is 77.2g.
(2) carbonating is separated silicic acid:
The sodium silicate solution that step (1) is obtained passes into carbonic acid gas and carries out carbonating, obtains sodium carbonate solution and siliceous colloid after the filtering separation.Sodium carbonate solution is obtained 69g yellow soda ash by the condensing crystal recovery.
(3) batching:
The residue that analytical procedure (1) obtains, alumina content are 45.7%, and dioxide-containing silica is 47.1%, and calculating the aluminium silicon mol ratio is 1.14, presses sodium al mole ratio 1.2, and the yellow soda ash 57g that gets step (2) recovery mixes with residue.Remaining yellow soda ash and sodium carbonate solution obtain sodium hydroxide solution after adding the unslaked lime causticization.
(4) sintering:
The batching that step (3) is obtained obtains sintered clinker at 850 ° of C sintering 3h.CO in the sintering process
2Can be back to the carbonating operation of step (2) in next circulation.
(5) hydrochloric acid acidleach:
With the sintered clinker hydrochloric acid soln acidleach that step (4) obtains, separate obtaining aluminum salt solution and siliceous colloid.
(6) alumina preparation:
Adding NaOH to pH in the aluminum salt solution that step (5) obtains is filtration in 6 o'clock, and filtrate is waste liquid, and the solid filtrate is Al (OH)
3And Fe (OH)
3Mixture, then this mixture is dissolved with NaOH, and to add alkali be to filter to pH that filtrate is NaAlO at 10 o'clock
2Solution, filter residue are Fe (OH)
3, with NaAlO
2Solution carbon divides acquisition Al (OH)
3, 110 ° of C dryings, 1200 ° of C calcinings obtain the 35.7g aluminum oxide.The content of aluminum oxide is 95.3%.
(7) white carbon black preparation:
Siliceous colloid washing, 110 ° of C dryings with step (2) and step (5) obtain get the 54.5g white carbon black, and wherein dioxide-containing silica is 90.6%.
As calculated, the extraction yield of aluminum oxide is 96.1%, and the extraction yield of silicon-dioxide is 96.3%.
Use 60g solid NaOH among this embodiment, the Na that uses 57g to reclaim in the process
2CO
3, remaining yellow soda ash and solution obtain NaOH solution after causticization, convert as solid NaOH to be about 17g.Be that the clean alkali number that uses in the reactivation process is 43g.Such as lixiviate SiO in advance not
2, then press aluminum oxide and silicon-dioxide in the flyash, activation needs to consume alkali (conversion is NaOH) 51.4g in theory, adds 20% loss, and alkaline consumption is 61.7g.Adopt the technology of the present invention, can economize on alkali about 30% in reactivation process.
Embodiment 2
Getting the 100g alumina content is 32.3%, and dioxide-containing silica is 56.3% flyash, according to step of the present invention:
(1) amorphous silicon di-oxide extracts:
Getting sodium hydroxide 75g, to be configured to mass concentration be 25% sodium hydroxide solution, and with the amorphous silicon di-oxide in this solution lixiviate flyash, at 110 ° of C reaction 5h, solid-liquid separation forms sodium silicate solution and residue, and the residue quality is 77.9g.
(2) carbonating is separated silicic acid:
The sodium silicate solution that step (1) is obtained passes into carbonic acid gas and carries out carbonating, obtains sodium carbonate solution and siliceous colloid after the filtering separation.Sodium carbonate solution is obtained 74g yellow soda ash by the condensing crystal recovery.
(3) batching:
The residue that analytical procedure (1) obtains, alumina content are 41.6%, and dioxide-containing silica is 45.5%, and calculating the aluminium silicon mol ratio is 1.07, presses sodium al mole ratio 1.3, and the yellow soda ash 56g that gets step (2) recovery mixes with residue.Remaining yellow soda ash and sodium carbonate solution obtain sodium hydroxide solution after adding the unslaked lime causticization.
(4) sintering:
The batching that step (3) is obtained obtains sintered clinker at 820 ° of C sintering 3h.CO in the sintering process
2Can be back to the carbonating operation of step (2) in next circulation.
(5) hydrochloric acid acidleach:
With the sintered clinker hydrochloric acid soln acidleach that step (4) obtains, separate obtaining aluminum salt solution and siliceous colloid.
(6) alumina preparation:
Adding NaOH to pH in the aluminum salt solution that step (5) obtains is filtration in 6 o'clock, and filtrate is waste liquid, and the solid filtrate is Al (OH)
3And Fe (OH)
3Mixture, then this mixture is dissolved with NaOH, and to add alkali be to filter to pH that filtrate is NaAlO at 10 o'clock
2Solution, filter residue are Fe (OH)
3, with NaAlO
2Solution carbon divides acquisition Al (OH)
3, 110 ° of C dryings, 1200 ° of C calcinings obtain the 31.9g aluminum oxide.The content of aluminum oxide is 96.4%.
(7) white carbon black preparation:
Siliceous colloid washing, 110 ° of C dryings that step (2) and step (5) are obtained make the 59.6g white carbon black, and wherein dioxide-containing silica is 91.1%.
As calculated, the extraction yield of aluminum oxide is 95.2%, and the extraction yield of silicon-dioxide is 96.3%.
Use 75g solid NaOH among this embodiment, the Na that uses 56g to reclaim in the reactivation process
2CO
3, remaining yellow soda ash and solution obtain NaOH solution after causticization, convert as solid NaOH to be about 33g.Be that the clean alkali number that uses in the reactivation process is 22g.Such as lixiviate SiO in advance not
2, then press aluminum oxide and silicon-dioxide in the flyash, activation needs to consume alkali (conversion is NaOH) 49.7g in theory, adds 20% loss, the about 60g of alkaline consumption.Adopt the technology of the present invention, can economize on alkali about 63%.
Embodiment 3
Getting the 100g alumina content is 28.2%, and dioxide-containing silica is 56.1% flyash, according to step of the present invention:
(1) amorphous silicon di-oxide extracts:
Getting sodium hydroxide 87.5g, to be configured to mass concentration be 35% sodium hydroxide solution, and with the amorphous silicon di-oxide in this solution lixiviate flyash, flyash and alkaline solution are by solid-to-liquid ratio 1:2.5, at 120 ° of C reaction 6h, solid-liquid separation forms sodium silicate solution and residue, and the residue quality is 82.7g.
(2) carbonating is separated silicic acid:
The sodium silicate solution that step (1) is obtained passes into carbonic acid gas and carries out carbonating, obtains sodium carbonate solution and siliceous colloid after the filtering separation.Sodium carbonate solution is obtained 82g yellow soda ash by the condensing crystal recovery.
(3) batching:
The residue that analytical procedure (1) obtains, alumina content are 33.7%, and dioxide-containing silica is 47.0%, and calculating the aluminium silicon mol ratio is 0.844, are 1.1[m by the molar weight of sodium
Al(slag)/51+2 (m
Si(slag)/60-m
Al(slag)/51)], the yellow soda ash 44g that gets step (2) recovery mixes with residue.Remaining yellow soda ash and sodium carbonate solution obtain sodium hydroxide solution after adding the unslaked lime causticization.。
(4) sintering:
The batching that step (3) is obtained obtains sintered clinker at 860 ° of C sintering 5h.
(5) hydrochloric acid acidleach:
With the sintered clinker hydrochloric acid soln acidleach that step (4) obtains, separate obtaining aluminum salt solution and siliceous colloid.
(6) alumina preparation:
Adding NaOH to pH in the aluminum salt solution that step (5) obtains is filtration in 6 o'clock, and filtrate is waste liquid, and the solid filtrate is Al (OH)
3And Fe (OH)
3Mixture, then this mixture is dissolved with NaOH, and to add alkali be to filter to pH that filtrate is NaAlO at 10 o'clock
2Solution, filter residue are Fe (OH)
3, with NaAlO
2Solution carbon divides acquisition Al (OH)
3, 110 ° of C dryings, 1200 ° of C calcinings obtain the 27.7g aluminum oxide.The content of aluminum oxide is 96.9%.
(7) white carbon black preparation:
Siliceous colloid washing, 110 ° of C dryings that step (2) and step (5) are obtained make the 63.2g white carbon black, and wherein dioxide-containing silica is 90.7%.
As calculated, the extraction yield of aluminum oxide is 94.9%, and the extraction yield of silicon-dioxide is 96.3%.
Reactivation process is used 87.5g solid NaOH altogether among this embodiment, recycles 44g Na in the process
2CO
3Be that the clean alkali number (conversion is NaOH) that uses in the reactivation process is 43.5g.Such as lixiviate SiO in advance not
2, then press aluminum oxide and silicon-dioxide in the flyash, activation needs to consume alkali (conversion is NaOH) 52.6g in theory, adds 20% loss, and alkaline consumption is 63.1g.Adopt the technology of the present invention, can economize on alkali about 45.1%.
Embodiment 4
Getting the 100g alumina content is 38.2%, and dioxide-containing silica is 48.7% flyash, according to step of the present invention:
(1) amorphous silicon di-oxide extracts:
Getting sodium hydroxide 75g, to be configured to mass concentration be 30% sodium hydroxide solution, and with the amorphous silicon di-oxide in this solution lixiviate flyash, at 130 ° of C reaction 5h, solid-liquid separation forms sodium silicate solution and residue, and the residue quality is 81.1g.
(2) carbonating is separated silicic acid:
The sodium silicate solution that step (1) is obtained passes into carbonic acid gas and carries out carbonating, obtains sodium carbonate solution and siliceous colloid after the filtering separation.Sodium carbonate solution is obtained 72g yellow soda ash by the condensing crystal recovery.
(3) batching:
The residue that analytical procedure (1) obtains, alumina content are 47.1%, and dioxide-containing silica is 37.9%, calculating the aluminium silicon mol ratio is 1.46, join the former flyash of 377g and obtain the aluminium silicon mol ratio and be about 1 flyash sample, press sodium al mole ratio 1.2,227g yellow soda ash is mixed with residue.
(4) sintering:
The batching that step (3) is obtained obtains sintered clinker at 820 ° of C sintering 3h.
(5) hydrochloric acid acidleach:
With the sintered clinker hydrochloric acid soln acidleach that step (4) obtains, separate obtaining aluminum salt solution and siliceous colloid.
(6) alumina preparation:
Adding NaOH to pH in the aluminum salt solution that step (5) obtains is filtration in 6 o'clock, and filtrate is waste liquid, and the solid filtrate is Al (OH)
3And Fe (OH)
3Mixture, then this mixture is dissolved with NaOH, and to add alkali be to filter to pH that filtrate is NaAlO at 10 o'clock
2Solution, filter residue are Fe (OH)
3, with NaAlO
2Solution carbon divides acquisition Al (OH)
3, 110 ° of C dryings, 1200 ° of C calcinings obtain the 38.4g aluminum oxide.The content of aluminum oxide is 95.8%.
(7) white carbon black preparation:
Siliceous colloid washing, 110 ° of C dryings that step (2) and step (5) are obtained make the 232g white carbon black, and wherein dioxide-containing silica is 90.3%.
As calculated, the extraction yield of aluminum oxide is 96.3%, and the extraction yield of silicon-dioxide is 95.7%.
Co-processing flyash 477g among this embodiment uses 75g solid NaOH and 227g yellow soda ash to be used for activation, reclaims 72g Na in the process
2CO
3Be that the clean alkali number (conversion is NaOH) that uses in the reactivation process is 192g.Such as lixiviate SiO in advance not
2, then press aluminum oxide and silicon-dioxide in the flyash, need in theory to consume alkali (conversion is NaOH) 172g, add 20% loss, alkaline consumption is 206g.Adopt the technology of the present invention, can economize on alkali about 6.8%.
Claims (5)
1. method of extracting aluminum oxide and white carbon black from flyash is characterized in that: comprise following steps,
(1) amorphous silicon di-oxide extracts: the amorphous silicon di-oxide with in the sodium hydroxide solution lixiviate flyash forms sodium silicate solution and residue;
(2) carbonating is separated silicic acid: the sodium silicate solution that step (1) is obtained passes into carbonic acid gas and carries out carbonating, obtain sodium carbonate solution and siliceous colloid after the filtering separation, sodium carbonate solution is by condensing crystal and add unslaked lime causticization recovery yellow soda ash and sodium hydroxide;
(3) batching: the residue that step (1) is obtained mixes with the yellow soda ash that former flyash and step (2) reclaim, and obtains batching;
(4) sintering: the batching sintering with step (3), obtain sintered clinker, the CO2 in the sintering process is back to the carbonating operation of step (2);
(5) hydrochloric acid acidleach: with the sintered clinker hydrochloric acid acidleach that step (4) obtains, separate obtaining aluminum salt solution and siliceous colloid;
(6) alumina preparation: the aluminum salt solution that step (5) is obtained obtains aluminum oxide by adding alkali removal of impurities, carbonization, drying, calcining;
(7) white carbon black preparation: with the siliceous colloid that step (2) and step (5) obtain wash, drying makes white carbon black.
2. a kind of method of extracting aluminum oxide and white carbon black from flyash according to claim 1 is characterized in that, the middle NaOH of described step (1) and flyash is 0.2 ~ 1:1 proportioning in mass ratio; The mass concentration of NaOH solution is 20-40%; Temperature of reaction is 80 ~ 150 ° of C.
3. a kind of method of extracting aluminum oxide and white carbon black from flyash according to claim 1 is characterized in that batching is according to Al in residue and the former flyash in the described step (3)
2O
3And SiO
2Content press the aluminium silicon mol ratio and determine, be specially:
I. work as aluminium silicon mol ratio in the residue〉1.2, residue and former flyash are made into compound in proportion, making aluminium silicon mol ratio wherein is 0.9 ~ 1.2; Yellow soda ash mixes by Na:Al mol ratio 1 ~ 2 with compound again;
Ii. the aluminium silicon mol ratio is 0.9 ~ 1.2 in residue, and residue is mixed by Na:Al mol ratio 1 ~ 2 with yellow soda ash;
Iii. residue and yellow soda ash are pressed first 1 ~ 2 times of [n of molar fraction of Na in aluminium silicon mol ratio＜0.9 in the residue
Al+ 2(n
Si-n
Al)] proportioning, wherein, n
AlAnd n
SiBe respectively the molar fraction of aluminium in the residue, silicon.
4. a kind of method of extracting aluminum oxide and white carbon black from flyash according to claim 1 is characterized in that sintering temperature is 700 ~ 950 ° of C in the described step (4).
5. according to claim 1 or 4 described a kind of methods of from flyash, extracting aluminum oxide and white carbon black, it is characterized in that sintering temperature is 800 ~ 900 ° of C in the described step (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310038565.4A CN103058239B (en) | 2013-01-30 | 2013-01-30 | Method of extracting aluminum oxide and white carbon black from pulverized fuel ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310038565.4A CN103058239B (en) | 2013-01-30 | 2013-01-30 | Method of extracting aluminum oxide and white carbon black from pulverized fuel ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103058239A true CN103058239A (en) | 2013-04-24 |
| CN103058239B CN103058239B (en) | 2014-10-08 |
Family
ID=48101178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310038565.4A Active CN103058239B (en) | 2013-01-30 | 2013-01-30 | Method of extracting aluminum oxide and white carbon black from pulverized fuel ash |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103058239B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420386A (en) * | 2013-08-05 | 2013-12-04 | 山西大学 | Method for preparing silica through coal gangue aluminum extraction waste slag |
| CN105668597A (en) * | 2014-11-21 | 2016-06-15 | 神华集团有限责任公司 | Method of acid-alkali combined extraction of aluminum-based products and silicon-based products from fly ash |
| CN108797207A (en) * | 2018-05-15 | 2018-11-13 | 仙鹤股份有限公司 | A kind of high-strength hot transfer body paper and its production method |
| CN112408401A (en) * | 2020-10-29 | 2021-02-26 | 中国建筑材料科学研究总院有限公司 | Method for preparing silicon dioxide aerogel by utilizing industrial solid waste fly ash and silicon dioxide aerogel prepared by method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284668A (en) * | 2007-04-12 | 2008-10-15 | 清华大学 | Process for abstracting earth silicon, oxide of alumina and gallium oxide from high-alumina flying ash |
| CN101306826A (en) * | 2008-06-20 | 2008-11-19 | 北京世纪地和科技有限公司 | Process for extracting metallurgy-level aluminum oxide from fly ash or slag |
| CN101759210A (en) * | 2010-01-18 | 2010-06-30 | 马昱昭 | Method for extracting high purity alumina and silica gel from coal ash |
-
2013
- 2013-01-30 CN CN201310038565.4A patent/CN103058239B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284668A (en) * | 2007-04-12 | 2008-10-15 | 清华大学 | Process for abstracting earth silicon, oxide of alumina and gallium oxide from high-alumina flying ash |
| CN101306826A (en) * | 2008-06-20 | 2008-11-19 | 北京世纪地和科技有限公司 | Process for extracting metallurgy-level aluminum oxide from fly ash or slag |
| CN101759210A (en) * | 2010-01-18 | 2010-06-30 | 马昱昭 | Method for extracting high purity alumina and silica gel from coal ash |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420386A (en) * | 2013-08-05 | 2013-12-04 | 山西大学 | Method for preparing silica through coal gangue aluminum extraction waste slag |
| CN105668597A (en) * | 2014-11-21 | 2016-06-15 | 神华集团有限责任公司 | Method of acid-alkali combined extraction of aluminum-based products and silicon-based products from fly ash |
| CN108797207A (en) * | 2018-05-15 | 2018-11-13 | 仙鹤股份有限公司 | A kind of high-strength hot transfer body paper and its production method |
| CN112408401A (en) * | 2020-10-29 | 2021-02-26 | 中国建筑材料科学研究总院有限公司 | Method for preparing silicon dioxide aerogel by utilizing industrial solid waste fly ash and silicon dioxide aerogel prepared by method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103058239B (en) | 2014-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102515279B (en) | Comprehensive extraction method of ferro-silico-aluminum in gangue | |
| CN101913632B (en) | Method for extracting aluminum oxide, monox and ferric oxide from gangue combustion ashes | |
| CN100457628C (en) | Method of extracting aluminium oxide from fly ash and simultaneously producing white carbon black | |
| CN101041450B (en) | Clean production technique for preparation of aluminium oxide and white carbon black by using high-alumina coal ash | |
| CN101941725B (en) | Method for extracting aluminum oxide from coal gangue and co-producing active calcium silicate | |
| CN102476820B (en) | Method for extracting alumina from coal ash through wet process | |
| CN101863500B (en) | Method for producing alumina with aluminum-containing metallurgical material | |
| WO2008119212A1 (en) | A method of extracting silica at first and then extracting alumina from fly ash | |
| CN103303952A (en) | Method for linked preparation of sodium aluminate and production of silica-based material by means of high-alumina fly ash low-temperature liquid-phase alkali dissolving | |
| CN101591197A (en) | A kind of method of utilizing pre-desiliconizing with high alumina fly ash to prepare calcium silicate fertilizer | |
| CN103058239B (en) | Method of extracting aluminum oxide and white carbon black from pulverized fuel ash | |
| CN102602969A (en) | Method for extracting aluminum oxide from fluidized bed coal ash | |
| CN102838147B (en) | Method for preparing mixed solution of sodium aluminate and potassium aluminate from alkaline syenite | |
| CN102757073B (en) | Method for producing aluminum oxide based on calcification-carbonization transformation | |
| CN103121700A (en) | Method for preparing ultrafine alumina and coproducing and white carbon black by utilizing coal series kaolin | |
| CN103663516B (en) | A kind of method utilizing aluminous fly-ash to prepare aluminium hydroxide | |
| CN103708479A (en) | Method for simultaneously preparing sodium metaaluminate and activated calcium metasilicate from coal ash | |
| CN101302021A (en) | Method for extracting aluminum oxide from fly ash | |
| CN104649279A (en) | Process for preparing white carbon black from pulverized fuel ash as raw material | |
| CN103421960A (en) | Method for efficiently recycling ferro-aluminium from bauxite tailings and synchronously preparing high siliceous residues | |
| CN100532266C (en) | Technique for producing hydrate alumina and silicic acid with coal ash | |
| CN103420406B (en) | Method for activating coal gangue and/or coal ash by using red mud | |
| CN101857250A (en) | Process for producing aluminium hydroxide, silicic acid and sodium carbonate by utilizing fly ash | |
| CN101857253B (en) | Process for producing aluminium hydroxide, silicic acid and sodium carbonate by utilizing fly ash | |
| CN100532264C (en) | Technique for producing hydroted alumina and silicic acid with coal gangue |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |